Congress Chair: Jeremy D. Glennon, University College Cork.
Organised by: Department of Chemistry, University College Cork.
Monday 26th November The Institute of Chemistry of Ireland Congress 2012 Devere Hall, UCC.
Final Program and Abstract Booklet
Sponsorship and Support
Platinum Sponsors: The organising committee gratefully acknowledges the corporate partner Waters Technologies Ireland Ltd. for their generous support of Congress 2012.
Exhibiting Sponsors: In addition, the participation and contribution of the following companies, vendors and organisations is much appreciated:
Chromatography and Separation methods continue to evolve to meet the many challenges that arise in industry, scientific discovery and research. The drive for new methods and materials is increasingly important as we continue to probe and understand the human genome, proteomics and metabolomics, and the many mechanistic pathways of life and in disease. Key aspects of pharmaceutical and bio-pharmaceutical research, development, production, quality control and product analysis and regulation, are fundamentally dependent upon separation science.
The theme of Congress 2012 “Chromatography Ireland” is chosen to reflect recent progress and activity in advancing the important field of separation science, and to invite you to join us for this unique one day meeting at University College Cork.
In addition to special new Institute membership offers available for registered participants, the Institute of Chemistry of Ireland invites you to join its new section, the Irish Chromatography & Separation Science Society.
http://www.masontechnology.ie/ http://www.sigmaaldrich.com/ireland.html
http://www.home.agilent.com/agilent/home.jspx?cc=IE&lc=eng http://www.glantreo.com
http://www.waters.com/waters/home.htm?locale
Monday 26th November 2012
08.00 - 9.00 Registration Desk open in Devere Hall
09.15 – 9.30 Welcome and Introductory Comments Prof. Jeremy D. Glennon (Congress 2012 Chair) Dr. Brian A. Murray (President, Institute of Chemistry of Ireland) Prof. Anita Maguire (Vice-President for Research & Innovation, UCC)
09.30 – 10.00 Prof. Apryll Stalcup, “What Surface-confined Ionic Liquids can tell us about Liquid Chromatography” ISSC, DCU.
10.00 – 10.30 Dr. Panagiotis Manesiotis, “Molecularly Imprinted Polymers: Advanced separation media with predetermined selectivity” PMBRC, WIT.
10.30 – 11.00 Dr. Martin Danaher, “Multi-residue analysis of contaminants in Food using (UHP)LC-MS/MS”, Food Safety Dept., Food Research Centre, Teagasc, Dublin.
11.00 – 11.30 AM Break – visit the Exhibits and Posters on display.
11.30 – 12.00 Dr. Richie Ryan, “Microemulsion Capillary Electrophoresis”, WIT.
12.00 - 12.30 Dr. Elizabeth Guihen, “Nanoparticles in Separation Science” Graduate Entry Medical School, Faculty of Education & Health Sciences, University of Limerick.
12.30 – 1.00 Dr. Craig Parnis, “UltraPerformance Convergence Chromatography (UPC2); Expanding Selectivity for the Chromatographic Laboratory” Waters Ltd.
1.00 – 2.30 Lunch, Exhibits and Posters Break
2.30 – 3.00 Dr. Brendan O’Connor, "Lectin Bioaffinity chromatography in Separation Science” School of Biotechnology, ISSC, DCU.
3.00 – 3.30 Prof. David Sheehan, “Redox proteomics: Trapping and enriching for oxidatively damaged proteins within proteomes” Biochemistry Dept., UCC.
3.30 – 4.00 Dr. Robert Frost, “Innovative Technologies for BioPharmaceutical Applications” Chemistry Operations, Waters Ltd.
4.00 – 4.30 PM Break Exhibits and Poster display 4.30 Congress 2012 close
Session 1: Chairman: Prof. Malcolm Smyth, DCU
Session 2: Chairman: Dr. Joe Power, WIT.
Session 3: Chairman: Prof. Jeremy D. Glennon
Poster Presentations (at time of printing):
Determination of Distribution Coefficients of Non Steroidal Anti-Inflammatory Drugs
(NSAID) by HPLC on Reverse Phase and Immobilized Artificial Membrane Columns
Owen Foley a, Dara Fitzpatrick a
a Innovative Chromatography Group, Irish Separation Science Cluster (ISSC), Department of Chemistry and Analytical, Biological Chemistry Research Facility (ABCRF), University College Cork, Ireland
The prediction of drug distribution in vivo is heavily dependent upon accurate partition co-
efficient (log P) or distribution co-efficient (log D) data for the successful application of
Pharmacokinetic and Quantitative Structure Activity Relationship (QSAR) models. The
Organization for Economic Co-operation and Development (OECD) stipulate that the
measurement of ionisable drug compound partition co-efficient data, obtained by HPLC on a
C18 column, be obtained at a pH where the ionisable drug is in it’s neutral form. However,
most in vivo environments are in pH ranges where weakly acidic drugs are partially or fully
ionised. Incorporation of log P guideline measurements results in a significant reduction in
the accuracy of the QSAR and Pharmacokinetic models.
The development of bio-mimetic Immobilized Artificial Membrane chromatography,
utilizing cellular membrane phospholipids as a stationary phase ligand, allows for increased
accuracy of in vivo applicable log P and log D value acquisition and the improvement of
QSAR modelling results.
Here, the distribution coefficients of a set Non Steroidal Anti-Inflammatory Drugs
(NSAID’s) including Indomethacin, Diclofenac, Flurbiprofen, Ketoprofen, Ibuprofen,
Naproxen, Sulindac, Ketorolac, Piroxicam and Fenoprofen, are determined on both IAM and
reverse phase columns across a range of pH values.
Sensitive Detection of Aminothiols in Serum by Silica Nanoparticle Modified Capillary
Electrophoresis Coupled with Boron Doped Diamond Electrode
Alyah Buzid a, Lin Zhou a, Jeremy D. Glennon a
a Innovative Chromatography Group, Irish Separation Science Cluster (ISSC), Department of Chemistry and Analytical, Biological Chemistry Research Facility (ABCRF), University College Cork, Ireland
Interest in the analysis and quantification of aminothiols has recently increased due to the
significance of their levels in biological fluids and tissues in diagnosing several human
pathologies. The Boron doped diamond electrode provides an easy method to detect
aminothiols sensitively without any derivatization. Thus, by combining a BDD electrode with
capillary electrophoresis, efficient separation and sensitive determination of N-acetyl-L-
cysteine, L-glutathione reduced, L-glutathione oxidized, L-cysteine, DL-homocysteine, L-
methionine, DL-homocystine and cysteine-glycine is achieved. Combined with off-line SPE
for sample pretreatment, it is a useful tool for the study of oxidative stress and redox
regulation. Glutathione is the most important thiol due to its role in protecting cells from
toxic species.
Differentiation of chiral isomers and isomeric ratios by Broadband Acoustic Resonance Dissolution Spectroscopy (BARDS) Rachel Evans-Hurson a, Dara Fitzpatrick a, Jacob Krüse a, Bastiaan Vos a
a Department of Chemistry and Analytical, Biological Chemistry Research Facility (ABCRF), University College Cork, Ireland
The dissolution of a compound results in the introduction and desolvation of gas in a solvent.
This process is due to gases adhered to or trapped within solid particles, and due to the
dissolving compound lowering the solubility of gases in the solvent. The presence of
desolvated gas increases the compressibility of the solvent, thereby reducing the velocity of
sound passing through it. This effect is monitored by means of the frequency changes of
mechanically induced acoustic resonances in the solvent. The response is strongly dependent
on the physical and chemical characteristics of the solute compound. Diastereomers and
epimeric compounds differ in physical properties and can produce variability in the response.
The utilisation of chiral solvents yields interactions with enantiomeric compounds and
produces variability in the acoustic effect, facilitating differentiation of enantiomers through a
simple dissolution test.
Supercritical Fluid vs. Organic Solvent as a Reaction Medium in Silica
Functionalisation
Amy Nagle a, Jeremy D. Glennon a, Helen Yeman b, Klaus Albert b a Innovative Chromatography Group, Irish Separation Science Cluster (ISSC), Department of Chemistry and Analytical & Biological Chemistry Research Facility (ABCRF), University College Cork, Ireland. b Universität Tübingen, Tübingen, Germany
A “green chemistry” approach for the preparation of silica bonded stationary phases has been
developed in our laboratory that avoids the use of problematic organic solvents. By exploiting
properties of supercritical carbon dioxide (sc-CO2), such as solvating power, lower toxicity
and enhanced diffusivity, organosilanes can be reacted with surface silanol groups, for the
clean, organic solvent-free synthesis of highly efficient silica bonded phases for liquid
chromatography (LC) and capillary electrochromatography (CEC). Spectroscopic analysis
including solid state NMR spectroscopy and chromatographic performance testing is used to
characterise the silica bonded phases generated. In this work we examine the preparation of a
silica hydride intermediate and of an octadecyl bonded silica stationary phase under
supercritical fluid conditions and compare the results to those prepared using traditional
organic solvents as the reaction medium.
Synthesis of 2.6 µm superficially porous particles and investigation of their kinetic
performance
Elaine M. Stack a, Jesse O. Omamogho a, Jeremy D. Glennon a a Innovative Chromatography Group, Irish Separation Science Cluster (ISSC), Department of Chemistry and Analytical, Biological Chemistry Research Facility (ABCRF), University College Cork, Ireland
Recent developments in particle technology have shown substantial interest in the use of
core-shell particles for liquid chromatography1. Sub-2 µm particles have been very popular
and well studied2 and we are now seeing a trend moving again towards larger particles. The
kinetic and chromatographic performance of two types of core-shell particles with an overall
diameter of 2.6 µm, packed in narrow bore columns was investigated in this work. The main
focus of the investigation was to look at the effect of the particle morphology, ie. the
roughness vs. smoothness of the core-shell particles, and also the effect of particle size
distribution on the overall efficiency of the column. To do this, Kinetex-2.6 µm-C18
columns (2.1 x 50 mm I.D and 2.1 x 100 mm I.D) was also studied as a comparison. [1] Omamogho, J. O.; Hanrahan, J. P.; Tobin, J.; Glennon, J. D. J. Chromatogr. A 2011, 1218, 1942.
[2] Gritti, F.; Omamogho, J.; Guiochon, G. J. Chromatogr. A 2011, 1218, 7078.
Synthesis and Characterisation of a Pentafluorophenylpropyl bonded silica stationary phase generated using supercritical carbon dioxide as a reaction solvent.
Benjamin A. Ashu-Arrah a, Jeremy D. Glennon a, Klaus Albert b
a Innovative Chromatography Group, Irish Separation Science Cluster (ISSC), Department of Chemistry, and the Analytical and Biological Chemistry Research Facility (ABCRF), University College Cork, Ireland. b Universität Tübingen, Institüt für Organische Chemie, D-72076 Tübingen, Germany.
The use of sc-CO2 for the synthesis of silica bonded phases has continued to attract greater
interest over the decade. Wide ranges of temperature and pressure programming conditions,
coupled with short reaction time and easily recycled reaction medium make sc-CO2 a viable
green chemistry alternative to conventional organic solvent based methods of preparation [1-
3]. Pentafluorophenyl propyl (PFPP) silica bonded stationary phase provide different
selectivity from C18 and phenyl stationary phases as the C-F bond is less polarisable than the
C-H bond [4]. The bonded PFPP was characterised by elemental analysis, thermogravimetric
analysis (TGA), scanning electron microscopy (SAM), and by solid-state NMR spectroscopy.
Chromatographic characterization and performance of the PFPP phase was also investigated
using the Neue test solute mixture. The results demonstrate that the PFPP phase can be
prepared successfully under supercritical conditions of 100°C, 414 bar in a reaction time of 1
h with surface coverage comparable to conventional organic solvent based methods.
Chromatography with Neue solute reveal rapid analysis within 7 min, coupled with a
different selectivity from C18 phases as evidenced in the elution of butylparaben and
dipropylphthalate before acenaphthene [4].
Fig. 1 Structure of silica bonded PFPP phases prepared in sc-CO2, reaction conditions:
100 ºC, 414 bar, 1 hour (3 μm Exsil-Pure silica). [1] B.A. Ashu-Arrah, J.D. Glennon, K. Albert, J. Chromatogr. A 1222 (2012) 38.
[2] B.A. Ashu-Arrah, J.D. Glennon, K. Albert, J. Chromatogr. A 1236 (2012) 42.
[3] C. Cao, A.Y. Fadeev, T.J. McCarthy, Langmuir 17 (2001) 757.
[4] B.A. Ashu-Arrah, J.D. Glennon, K. Albert, Manuscript No. JCA-12-1031. in print (2012)
Analysis of Neuroendocrine Tumor Markers by Hydrophilic Interaction Liquid
Chromatography (HILIC)
Fengjun Shang a, Victor Langsi a, Jeremy D. Glennon a a Innovative Chromatography Group, Irish Separation Science Cluster (ISSC), Department of Chemistry and the Analytical and Biological Chemistry Research Facility (ABCRF), University College Cork, Cork, Ireland.
Neuroblastoma, a neoplastic disease of early childhood, is the third most common cancer in
children. Measurements of catecholamine metabolites homovanillic acid (HVA) and
vanylmandelic acid (VMA) serve as a screening test for neuroblastoma [1]. The metabolism
of serotonin to 5-hydroxyindole-3-acetic acid (5-HIAA) is a diagnostic marker in urine for
the ‘carcinoid syndrome’ [2]. Hydrophilic interaction liquid chromatography (HILIC)
provides an alternative approach to effectively separate polar drugs, metabolites and
biologically important compounds in proteomics, glycomics and clinical analysis. In this
study, a rapid and sensitive method was developed to separate and quantify HVA, VMA and
5-HIAA using a ZIC-HILIC column. A set of nucleobases/nucleosides were employed to
evaluate chromatographic properties of the sulfobetaine HILIC stationary phases. The
retention mechanism of the column was investigated by adjusting the ratio of water in the
mobile phase, salt concentration, buffer pH and ionic strength.
[1] Tsubono, Y.; Hisamichi, S. N. Engl. J. Med. 2004, 350, 2010-2011. [2] Manickum, T. J.
Chromatogr. B 2009, 877, 4140-4146.
Capillary Electrophoresis with a Boron Doped Diamond Electrode for Trace Detection
of Endocrine Disruptors in Water Samples
Damien J. Browne a, Lin Zhou a, John H.T. Luong b, Jeremy D. Glennon a
a Innovative Chromatography Group, Irish Separation Science Cluster (ISSC), Department of Chemistry and Analytical, Biological Chemistry Research Facility (ABCRF), University College Cork, Ireland. b National Research Council Canada, Montreal, Quebec, Canada.
Off-line solid-phase extraction-capillary electrophoresis coupled with electrochemical
detection (SPE-CE-ECD) has been used for the determination of bisphenol A (BPA),
bisphenol F (BPF), 4-ethylphenol (4-EP) and bisphenol A diglycidyl ether (BADGE) in
bottled drinking water. A key to the sensitive, reproducible, and stable detection of these
endocrine-disrupting compounds was the use of a boron doped diamond (BDD) electrode in
the amperometric mode. An off-line SPE procedure was utilized to extract and pre-
concentrate the compounds prior to separation and detection with Bond Elut C18 as the
sorbent. The oxidative detection of the endocrine-disrupting compounds was accomplished at
+1.4 V vs Ag/AgCl without electrode pretreatment. The minimum concentration detectable
for all four compounds ranged ~ 0.01 µM (S/N=3), or ~2.5 ppb using a 100:1
preconcentration factor. After exposing the plastic bottle water container under sunlight for a
week, the estimated concentration of BPA in the drinking water was 0.03 µM. This proposed
approach was rapid and effective for the determination of BPA present in bottled water.
Separation of Biomarkers by Micro-Electrophoresis with Chemiluminescence and
Electrochemical Detection in Toner-Based Microchips
Una Crowley a, E. Moore a,b, Jeremy D. Glennon a
a Innovative Chromatography Group, Irish Separation Science Cluster (ISSC), Department of Chemistry and Analytical, Biological Chemistry Research Facility (ABCRF), University College Cork, Ireland. b Life Sciences Interface Group, Tyndall National Institute, Lee Maltings, Dyke Parade, Cork, Ireland.
Since the introduction of micro-total analytical systems (μTAS) and lab-on-a-chip technology,
microfluidic devices have been applied in almost every area of separation science. In this
work, a laser printer is used to selectively deposit toner onto polyester film, and the resulting
toner-based microchips are coupled with several detection methods, particularly Chip-
Electrophoresis-Chemiluminescence (CE-CL) detection and Chip-Electrophoresis-
Electrochemical detection (CE-EC). The detection limit of selected biomarkers can be as low
as 1μM and the baseline separation is achieved within 60 seconds.
In addition, we have developed a range of micro-electrodes made of gold, silver and
platinum by means of patterning and deposition techniques onto acetate. These electrodes
have been designed for in-channel detection using toner-based microchips.
Fig. 1. View of toner microchip design for CE-CL Fig. 2. Representation of the
sensor design
Acknowledgements:
Scientific Organising Committee:
• Eileen O’Callaghan, Manager Chemistry Department, UCC. • Amy Nagle, Innovative Chromatography Group, ISSC and ABCRF, Department of Chemistry,
UCC. • Dr. Matthias Jauch, Systems Officer, Department of Chemistry, UCC. • Prof. Jeremy D. Glennon, Innovative Chromatography Group, ISSC and ABCRF, Department
of Chemistry, UCC. • Dr. Dara Fitzpatrick, Analytical Division, ISSC and ABCRF, Department of Chemistry, UCC. • Dr. Mila Pravda, Analytical Division, ISSC and ABCRF, Department of Chemistry, UCC. • Dr. Eric Moore, Analytical Division, ISSC and ABCRF, Department of Chemistry, UCC.
The committee would like to specifically thank the invited speakers, all of the researchers and staff of the Innovative Chromatography Group, the ISSC at UCC and DCU, ABCRF at UCC and Department of Chemistry, UCC, as well as Elaine Tynan, Graduate Manager, Aras na Mac Leinn, University College Cork.
Useful Websites and links:
Chemistry UCC website http://chemistry.ucc.ie
Institute of Chemistry of Ireland http://www.chemistryireland.org/
Research Centres:
Irish Separation Science Cluster (ISSC )
www.separationscience.ie
ABCRF website http://abcrf.ucc.ie
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